WO2017037984A1 - 気体センサ、及び燃料電池自動車 - Google Patents

気体センサ、及び燃料電池自動車 Download PDF

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Publication number
WO2017037984A1
WO2017037984A1 PCT/JP2016/003178 JP2016003178W WO2017037984A1 WO 2017037984 A1 WO2017037984 A1 WO 2017037984A1 JP 2016003178 W JP2016003178 W JP 2016003178W WO 2017037984 A1 WO2017037984 A1 WO 2017037984A1
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Prior art keywords
electrode
metal oxide
gas
gas sensor
oxide layer
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PCT/JP2016/003178
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English (en)
French (fr)
Japanese (ja)
Inventor
本間　運也
魏　志強
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パナソニックＩｐマネジメント株式会社
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Application filed by パナソニックＩｐマネジメント株式会社 filed Critical パナソニックＩｐマネジメント株式会社
Priority to JP2016570055A priority Critical patent/JP6145762B1/ja
Priority to EP16826277.2A priority patent/EP3343212B1/en
Priority to CN201680002015.9A priority patent/CN108112263B/zh
Priority to US15/416,000 priority patent/US10794848B2/en
Publication of WO2017037984A1 publication Critical patent/WO2017037984A1/ja

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/122—Circuits particularly adapted therefor, e.g. linearising circuits
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/03—Fuel tanks
    • B60K15/063—Arrangement of tanks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/70—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by fuel cells
    • B60L50/71—Arrangement of fuel cells within vehicles specially adapted for electric vehicles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/70—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by fuel cells
    • B60L50/72—Constructional details of fuel cells specially adapted for electric vehicles
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/128—Microapparatus
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0444—Concentration; Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/03—Fuel tanks
    • B60K2015/0321—Fuel tanks characterised by special sensors, the mounting thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/03—Fuel tanks
    • B60K2015/03309—Tanks specially adapted for particular fuels
    • B60K2015/03315—Tanks specially adapted for particular fuels for hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
    • B60K15/00—Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/03—Fuel tanks
    • B60K15/063—Arrangement of tanks
    • B60K2015/0638—Arrangement of tanks the fuel tank is arranged in the rear of the vehicle
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/0047—Organic compounds
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004—Gaseous mixtures, e.g. polluted air
    • G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
    • G01N33/005—H2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
    • H01M2250/20—Fuel cells in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/04664—Failure or abnormal function
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02T90/40—Application of hydrogen technology to transportation, e.g. using fuel cells

Definitions

  • the present disclosure relates to a gas sensor for detecting gas molecules including hydrogen atoms contained in a gas, and a fuel cell vehicle including the same.
  • Patent Document 1 discloses a gas sensor having an MIM structure in which a metal film, a gas sensitive resistance film, and a metal film are laminated.
  • the gas sensor of Patent Document 1 uses an insulating film obtained by adding a predetermined amount of palladium (Pd) and glass to tantalum pentoxide (Ta 2 O 5 ) as a gas-sensitive resistive film, and the gas-sensitive resistive film is made of platinum (Pt ) Is sandwiched between upper and lower metal electrodes.
  • Patent Document 1 describes that the gas sensor can detect a combustible gas containing hydrogen (hereinafter referred to as a hydrogen-containing gas).
  • Non-Patent Document 1 discloses a gas sensor having a MIS structure in which a metal, a gas-sensitive resistive film, and a semiconductor are stacked.
  • the gas sensor of Non-Patent Document 1 is composed of a laminate of Pt, Ta 2 O 5 , and silicon (Si) or silicon carbide (SiC), and detects a gas containing hydrogen atoms.
  • Non-Patent Document 1 discloses a change in electrical characteristics caused by reduction of Ta 2 O 5 in a gas-sensitive resistive film by hydrogen atoms dissociated from a hydrogen-containing gas by the catalytic action of Pt (for example, IV characteristics of MIS structure). Is used to detect a hydrogen-containing gas.
  • Patent Document 1 describes that the gas sensor is heated to 400 ° C.
  • Non-Patent Document 1 describes that the gas sensor is heated from 100 ° C. to 150 ° C.
  • the conventional gas sensor uses a heater in order to obtain good detection sensitivity for hydrogen-containing gas, there is a problem that power consumption is large.
  • One embodiment of the present disclosure provides a gas sensor excellent in power saving for detecting a hydrogen-containing gas.
  • the gas sensor which concerns on 1 aspect of this indication is a gas sensor for detecting the gas molecule containing the hydrogen atom contained in gas, Comprising: The 1st main surface and the said 1st main surface and the opposite side A first electrode having a second main surface; a third main surface opposite to the second main surface of the first electrode; and a fourth main surface opposite to the third main surface. A second electrode having the second main surface of the first electrode and the third main surface of the second electrode, the second main surface being disposed between the first electrode and the second electrode.
  • the gas sensor according to one embodiment of the present disclosure can detect a hydrogen-containing gas without being heated by a heater, and thus has excellent power saving performance.
  • FIG. 1A is a cross-sectional view of the gas sensor according to Embodiment 1.
  • FIG. 1B is a top view of the gas sensor according to Embodiment 1.
  • FIG. 2A is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 1.
  • FIG. 2B is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 1.
  • FIG. 2C is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 1.
  • FIG. 2D is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 1.
  • FIG. 2E is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 1.
  • FIG. 1A is a cross-sectional view of the gas sensor according to Embodiment 1.
  • FIG. 1B is a top view of the gas sensor according to Embodiment 1.
  • FIG. 2A is a cross-section
  • FIG. 2F is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 1.
  • FIG. 2G is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 1.
  • FIG. 3 is a diagram illustrating state transition of the gas sensor according to the first embodiment.
  • FIG. 4 is a cross-sectional view of a gas sensor according to a modification of the first embodiment.
  • FIG. 5A is a diagram showing a gas sensor evaluation system according to a modification of the first embodiment.
  • FIG. 5B is a diagram showing an evaluation result of the gas sensor according to the modification of the first embodiment.
  • 6A is a cross-sectional view of the gas sensor according to Embodiment 2.
  • FIG. 6B is a top view of the gas sensor according to Embodiment 2.
  • FIG. 7A is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 7B is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 7C is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 7D is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 7E is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 7F is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 7A is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 7B is a cross-sectional view illustrating the method for manufacturing the gas sensor according
  • FIG. 7G is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 7H is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 7I is a cross-sectional view illustrating the method for manufacturing the gas sensor according to the second embodiment.
  • FIG. 7J is a cross-sectional view illustrating the method for manufacturing the gas sensor according to Embodiment 2.
  • FIG. 8 is a cross-sectional view of a gas sensor according to Modification 1 of Embodiment 2.
  • FIG. 9 is a cross-sectional view of a gas sensor according to Modification 2 of Embodiment 2.
  • FIG. 8 is a cross-sectional view of a gas sensor according to Modification 1 of Embodiment 2.
  • FIG. 9 is a cross-sectional view of a gas sensor according to Modification 2 of Embodiment 2.
  • FIG. 10A is a cross-sectional view illustrating the method of manufacturing the gas sensor according to the second modification of the second embodiment.
  • FIG. 10B is a cross-sectional view illustrating the method for manufacturing the gas sensor according to the second modification of the second embodiment.
  • FIG. 10C is a cross-sectional view illustrating the method for manufacturing the gas sensor according to the second modification of the second embodiment.
  • FIG. 10D is a cross-sectional view illustrating the method for manufacturing the gas sensor according to the second modification of the second embodiment.
  • FIG. 10E is a cross-sectional view illustrating the method of manufacturing the gas sensor according to the second modification of the second embodiment.
  • FIG. 10F is a cross-sectional view illustrating the method for manufacturing the gas sensor according to the second modification of the second embodiment.
  • FIG. 10G is a cross-sectional view illustrating the method of manufacturing the gas sensor according to the second modification of the second embodiment.
  • FIG. 10H is a cross-sectional view illustrating the method for manufacturing the gas sensor according to the second modification of the second embodiment.
  • FIG. 10I is a cross-sectional view illustrating the method for manufacturing the gas sensor according to the second modification of the second embodiment.
  • FIG. 11 is a cross-sectional view of a gas sensor according to Modification 3 of Embodiment 2.
  • FIG. 12 is a side view of the fuel cell vehicle according to Embodiment 3.
  • the conventional gas sensor has the following problems.
  • the element for detecting the gas in order to improve the sensitivity for detecting the hydrogen-containing gas, the element for detecting the gas is heated to 100 ° C. or higher, and the power consumption is about 100 mW even at the minimum. Therefore, when the gas sensor is always used in an ON state, there is a problem that power consumption increases.
  • the present disclosure provides a gas sensor that detects a hydrogen-containing gas and is excellent in power saving.
  • the gas sensor which concerns on 1 aspect of this indication is a gas sensor for detecting the gas molecule containing the hydrogen atom contained in gas, Comprising: The 1st main surface and the said 1st main surface and the opposite side A first electrode having a second main surface; a third main surface opposite to the second main surface of the first electrode; and a fourth main surface opposite to the third main surface. A second electrode having the second main surface of the first electrode and the third main surface of the second electrode, the second main surface being disposed between the first electrode and the second electrode.
  • the metal oxide layer includes a local region in contact with the second electrode, and the oxygen deficiency of the metal oxide included in the local region is determined by the metal oxidation. It may be larger than the oxygen deficiency of the metal oxide contained in the portion of the physical layer excluding the local region.
  • the second electrode may contain a material having a catalytic action to dissociate hydrogen atoms from gas molecules containing hydrogen atoms.
  • a resistance value between the first electrode and the second electrode decreases. To do. By this change in resistance value, it is possible to detect that gas molecules having hydrogen atoms are contained in the gas to be measured.
  • the current flowing between the first electrode and the second electrode is concentrated in a local region including a metal oxide having a high degree of oxygen deficiency.
  • the temperature of the local region can be increased with a small current. This makes it possible to detect hydrogen-containing gas without heating with a heater by utilizing self-heating and gas sensitivity in the local region located inside the metal oxide layer, and a gas sensor with excellent power saving Is obtained.
  • gas containing gas molecules containing hydrogen atoms examples include gas containing hydrogen, methane, alcohol and the like.
  • the local region is in contact with the local region of the second electrode by generating heat due to a current flowing between the first electrode and the second electrode.
  • Hydrogen atoms are dissociated from the gas molecules in the part.
  • the dissociated hydrogen atoms are combined with oxygen atoms in the local region of the metal oxide layer, so that the resistance value of the metal oxide layer is reduced.
  • the temperature of the surface of the second electrode increases.
  • the efficiency of dissociating hydrogen atoms from gas molecules having hydrogen atoms at the second electrode is improved by the catalytic action of the second electrode.
  • the first electrode and the second electrode that are disposed so that the principal surfaces face each other, and the principal surface of the first electrode and the principal surface of the second electrode are disposed in contact with each other.
  • a hydrogen detection method using a gas sensor comprising a metal oxide layer wherein a gas containing a gas molecule having a hydrogen atom is in contact with the second electrode, and the first electrode and the first electrode You may make it detect the gas molecule which has the said hydrogen atom with the resistance value between 2 electrodes falling.
  • the metal oxide layer of the gas sensor generates heat only by passing a current for detecting the resistance value of the metal oxide layer, so that a hydrogen-containing gas is detected without heating with a separate heater. it can.
  • the hydrogen-containing gas can be detected by a gas sensor in which the local region is in either a high resistance state or a low resistance state.
  • the resistance value of the gas sensor is higher than that of the high resistance state and the high resistance state so that the metal oxide layer of the gas sensor can transition reversibly so that a decrease in the resistance value of the metal oxide layer can be detected more clearly.
  • the metal oxide layer may be set to the high resistance state, and the gas sensor may be brought into contact with the second electrode.
  • the gas sensor which concerns on 1 aspect of this indication WHEREIN The said metal oxide layer is compared with the high resistance state and the said high resistance state based on the voltage applied between the said 1st electrode and the said 2nd electrode.
  • a transition may be made reversibly between a low resistance state with a low resistance value.
  • the local region can be electrically set to a high resistance state.
  • the metal oxide layer has a first metal oxide layer containing the first metal oxide and an oxygen deficiency as compared with the first metal oxide.
  • the local region penetrates at least the second metal oxide layer, and the oxygen deficiency of the metal oxide contained in the local region is determined by the second metal oxide. It may be larger than the degree of oxygen deficiency.
  • the second electrode may contain at least one selected from the group consisting of platinum, palladium, and an alloy of platinum and palladium.
  • each of the first metal oxide and the second metal oxide may be a transition metal oxide or an aluminum oxide.
  • the transition metal oxide may be one selected from the group consisting of tantalum oxide, hafnium oxide, and zirconium oxide.
  • a gas sensor includes a via that is connected to the second electrode through a portion of the insulating film that covers the second electrode, and a conductor that is connected to the via. And may be further provided.
  • the via may be disposed at a position that is not directly above the first electrode.
  • a gas sensor having excellent resistance change characteristics and high reliability can be obtained by employing a suitable structure and material.
  • the gas sensor which concerns on 1 aspect of this indication WHEREIN The area which the said 2nd main surface of the said 1st electrode and the said metal oxide layer contact
  • the outline of the first electrode can be provided at a desired position in the second electrode in a top view. Since the local region is likely to be formed on the contour of the first electrode, there is a concern that the response time may be impaired, for example, directly below an upper structure such as a connection via, depending on the contour position of the first electrode. The local region can be formed avoiding a certain position. Thereby, the gas sensor excellent in responsiveness is obtained.
  • the gas sensor according to an aspect of the present disclosure further includes a measurement circuit that measures a current flowing through the metal oxide layer when a voltage is applied between the first electrode and the second electrode. May be.
  • the gas sensor according to one embodiment of the present disclosure may further include a power supply circuit that applies a voltage between the first electrode and the second electrode.
  • the power supply circuit may be configured such that a voltage is always applied between the first electrode and the second electrode.
  • a highly convenient gas sensor can be obtained as a module component including a measurement circuit or a power supply circuit.
  • a fuel cell vehicle includes a guest room, a gas tank chamber in which a hydrogen gas tank is disposed, a fuel cell chamber in which a fuel cell is disposed, and a gas sensor according to one embodiment of the present disclosure.
  • the gas sensor is arranged in at least one selected from the group consisting of the gas tank chamber and the fuel cell chamber.
  • the gas sensor may be used for hydrogen detection in a passenger compartment of the fuel cell vehicle.
  • a voltage is constantly applied to the gas sensor, and based on the amount of current flowing through the gas sensor, the outside of the tank in the gas tank chamber in which the hydrogen gas tank is disposed, and It may be determined whether or not hydrogen atoms are present in at least one of the outside of the fuel cell in the fuel cell chamber in which the fuel cell is disposed.
  • the gas sensor is driven to determine the presence or absence of fuel gas leakage after receiving the operation of the ignition key.
  • the start time of the fuel cell vehicle can be shortened.
  • safety can be improved by continuously monitoring the fuel gas leakage.
  • all or part of a unit, device, member, or part, or all or part of a functional block in a block diagram includes a semiconductor device, a semiconductor integrated circuit (IC), or an LSI (large scale integration). It may be performed by one or more electronic circuits.
  • the LSI or IC may be integrated on a single chip, or may be configured by combining a plurality of chips.
  • the functional blocks other than the memory element may be integrated on one chip.
  • LSI and IC are called.
  • the name changes depending on the degree of integration, and may be called system LSI, VLSI (very large scale integration), or ULSI (ultra large scale integration).
  • Field programmable gate array Field Programmable Gate Array: FPGA
  • FPGA Field Programmable Gate Array
  • reconfigurable logic device that can reconfigure the junction relationship inside LSI or set up circuit partitions inside LSI (Reconfigurable logic device) can also be used for the same purpose.
  • the software is recorded on a non-transitory recording medium such as one or more ROMs, optical disks, hard disk drives, etc., and is specified by the software when the software is executed by a processor.
  • Functions are performed by a processor and peripheral devices.
  • the system or apparatus may include one or more non-transitory recording media on which software is recorded, a processor, and required hardware devices, such as an interface.
  • the gas sensor according to the first embodiment is a gas sensor having a metal-insulating film-metal (MIM) structure in which a gas-sensitive resistive film that is a metal oxide layer and a metal film are laminated.
  • the gas sensor can detect a hydrogen-containing gas without heating with a heater by utilizing self-heating in a local region formed in the gas-sensitive resistive film and gas sensitivity.
  • the hydrogen-containing gas is a general term for gases composed of molecules having hydrogen atoms, and as an example, may include hydrogen, methane, alcohol, and the like.
  • FIG. 1A is a cross-sectional view showing a configuration example of the gas sensor 100 according to the first embodiment.
  • FIG. 1B is a top view showing a configuration example of the gas sensor 100 according to the first embodiment.
  • the cross section in FIG. 1A corresponds to the cross section seen in the direction of the arrow along the cutting line 1A-1A in FIG. 1B.
  • the gas sensor 100 includes a substrate 101, an insulating film 102 disposed on the substrate 101, a first electrode 103, a second electrode 106, a first electrode 103, and a second electrode disposed above the insulating film 102.
  • the first electrode 103 has a first main surface that is a lower surface and a second main surface that is an upper surface.
  • the second electrode 106 has a third main surface that is a lower surface and a fourth main surface that is an upper surface.
  • the second main surface of the first electrode 103 and the third main surface of the second electrode 106 are arranged to face each other, and the second main surface of the first electrode 103 and the second main surface of the second electrode 106 are arranged.
  • the gas sensitive resistive film 104 is disposed in contact with the main surface 3.
  • the interlayer insulating film 107 is provided with an opening 107a for bringing the second electrode 106 into contact with a gas to be inspected.
  • the interlayer insulating film 107 covers at least the fourth main surface that is the upper surface of the second electrode 106 while covering the first electrode 103, part of the second electrode 106, and the gas-sensitive resistive film 104. A part of the film is not covered with the interlayer insulating film 107 and is exposed to the gas to be inspected.
  • the interlayer insulating film 107 covers the entire first electrode 103 and the entire gas-sensitive resistance film 104, but the present disclosure is not limited to this configuration.
  • the interlayer insulating film 107 may partially cover the first electrode 103 and the gas sensitive resistance film 104, respectively.
  • the gas sensitive resistance film 104 is disposed between the first electrode 103 and the second electrode 106.
  • the gas-sensitive resistance film 104 is a layer whose resistance value reversibly changes based on an electrical signal applied between the first electrode 103 and the second electrode 106.
  • the gas-sensitive resistive film 104 has a high voltage depending on the voltage applied between the first electrode 103 and the second electrode 106 and the presence or absence of a hydrogen-containing gas in the gas in contact with the second electrode 106. Reversibly transition between a resistance state and a low resistance state.
  • a local region 105 that is in contact with the second electrode 106 and is not in contact with the first electrode 103 is provided inside the gas-sensitive resistive film 104.
  • the oxygen deficiency of the metal oxide contained in the local region 105 is larger than the oxygen deficiency of the metal oxide contained in a portion other than the local region 105 of the gas sensitive resistance film 104.
  • the oxygen deficiency of the metal oxide contained in the local region 105 depends on the application of an electrical signal applied between the first electrode 103 and the second electrode 106 and the hydrogen in the gas in contact with the second electrode 106. It changes reversibly according to the presence or absence of the contained gas.
  • the local region 105 is a minute region including a filament composed of oxygen defect sites. The filament functions as a conductive path.
  • a via 108 is disposed in a portion of the interlayer insulating film 107 that covers the second electrode 106.
  • the via 108 penetrates through the interlayer insulating film 107 and is connected to the second electrode 106.
  • a wiring conductor 109 is disposed on the via 108.
  • oxygen deficiency refers to the ratio of oxygen deficiency to the amount of oxygen contained in an oxide having a stoichiometric composition in a metal oxide.
  • the stoichiometric composition of the metal oxide in this specification is the chemistry having the highest resistance value. Means stoichiometric composition.
  • a metal oxide having a stoichiometric composition is more stable and has a higher resistance value than a metal oxide having another composition.
  • the stoichiometric oxide according to the above definition is Ta 2 O 5 .
  • Ta 2 O 5 can also be expressed as TaO 2.5 .
  • the degree of oxygen deficiency of TaO 2.5 is 0%.
  • the oxygen excess metal oxide has a negative oxygen deficiency.
  • the oxygen deficiency includes a positive value, 0, and a negative value.
  • a metal oxide with a low degree of oxygen deficiency has a high resistance value because it is closer to a metal oxide having a stoichiometric composition, and a metal oxide with a high degree of oxygen deficiency has a resistance value because it is closer to the metal that is a component of the metal oxide. Low.
  • Oxygen content is the ratio of oxygen atoms to the total number of atoms.
  • the oxygen content of Ta 2 O 5 is the ratio of oxygen atoms to the total number of atoms (O / (Ta + O)), which is 71.4 atm%. Accordingly, the oxygen content of the oxygen-deficient tantalum oxide is greater than 0 and less than 71.4 atm%.
  • the local region 105 is formed in the gas sensitive resistance film 104 by applying an initial break voltage between the first electrode 103 and the second electrode 106.
  • the initial break voltage is applied between the first electrode 103 and the second electrode 106 in order to reversibly transition the gas sensitive resistance film 104 between the high resistance state and the low resistance state. It may be a voltage having an absolute value larger than a normal write voltage.
  • the initial break voltage may be a voltage whose absolute value is smaller than the write voltage. In this case, the initial break voltage may be repeatedly applied or continuously applied for a predetermined time. By applying the initial break voltage, a local region 105 that is in contact with the second electrode 106 and is not in contact with the first electrode 103 is formed in the gas-sensitive resistive film 104 as shown in FIG. 1A.
  • the local region 105 is considered to include a filament composed of oxygen defect sites.
  • the size of the local region 105 is a minute size suitable for a filament necessary for flowing current. Filament formation in the local region 105 is described using a percolation model.
  • the percolation model assumes a random distribution of oxygen defect sites (hereinafter simply referred to as defect sites) in the local region 105, and the probability that defect site connections are formed when the density of defect sites exceeds a certain threshold. It is a model based on the theory that increases.
  • the filament is configured by connecting a plurality of defect sites in the local region 105. Further, according to the percolation model, the resistance change in the gas-sensitive resistive film 104 is expressed through the generation and disappearance of defect sites in the local region 105.
  • defect means that oxygen is missing from the stoichiometric composition in the metal oxide.
  • Defect site density corresponds to the degree of oxygen deficiency. That is, as the oxygen deficiency increases, the density of defect sites also increases.
  • Only one local region 105 may be formed on the gas-sensitive resistive film 104 of the gas sensor 100.
  • the number of local regions 105 in the gas-sensitive resistive film 104 can be confirmed by, for example, EBAC (Electron Beam Absorbed Current) analysis.
  • the local region 105 in the gas sensitive resistance film 104, when a voltage is applied between the first electrode 103 and the second electrode 106, the current in the gas sensitive resistance film 104 is changed to the local region. 105 intensively flows.
  • the local region 105 Due to its small size, the local region 105, for example, generates a considerable amount of heat due to a current of about several tens of ⁇ A (that is, power consumption of less than 0.1 mW) when a voltage of about 1 V is applied to read out the resistance value. A temperature rise occurs.
  • ⁇ A that is, power consumption of less than 0.1 mW
  • the second electrode 106 is made of a catalytic metal, for example, Pt, and the portion of the second electrode 106 that is in contact with the local region 105 is heated by the heat generated in the local region 105, so that the hydrogen-containing gas is removed. Increase the efficiency of dissociation of hydrogen atoms.
  • the gas sensor 100 has a characteristic that the resistance value of the gas-sensitive resistive film 104 decreases when the second electrode 106 comes into contact with the hydrogen-containing gas. Due to the characteristics, the gas to be inspected is brought into contact with the second electrode 106, and the resistance value between the first electrode 103 and the second electrode 106 decreases, so that the hydrogen-containing gas contained in the gas is reduced. Can be detected.
  • the hydrogen-containing gas can be detected by the gas sensor 100 in which the local region 105 is in either the high resistance state or the low resistance state.
  • the gas sensor 100 in which the local region 105 is electrically set in advance in a high resistance state may be used so that a decrease in the resistance value can be detected more clearly.
  • the gas sensitive resistance film 104 contains an oxygen-deficient metal oxide.
  • the base metal of the metal oxide is tantalum (Ta), hafnium (Hf), titanium (Ti), zirconium (Zr), niobium (Nb), tungsten (W), nickel (Ni), iron (Fe), etc. At least one may be selected from the group consisting of a transition metal and aluminum (Al). Since transition metals can take a plurality of oxidation states, different resistance states can be realized by oxidation-reduction reactions.
  • the oxygen-deficient metal oxide refers to a metal oxide having an oxygen content (atomic ratio) smaller than that of a metal oxide having a stoichiometric composition, which is usually an insulator. Many oxygen-deficient metal oxides usually behave like semiconductors.
  • the gas sensor 100 can realize a resistance change operation with good reproducibility and stability.
  • the resistance of the gas sensitive resistance film 104 is The value can be changed stably.
  • the film thickness of the hafnium oxide may be 3 to 4 nm.
  • the thickness of the zirconium oxide may be 1 to 5 nm.
  • the resistance value of the gas sensitive resistive film 104 is Can be changed stably.
  • composition of each metal oxide layer can be measured using Rutherford backscattering method.
  • the material of the first electrode 103 and the second electrode 106 is, for example, Pt (platinum), Ir (iridium), Pd (palladium), Ag (silver), Ni (nickel), W (tungsten), Cu (copper) ), Al (aluminum), Ta (tantalum), Ti (titanium), TiN (titanium nitride), TaN (tantalum nitride), TiAlN (titanium nitride aluminum), and the like.
  • a material of the second electrode 106 for example, a material having a catalytic action of dissociating a hydrogen atom from a gas molecule having a hydrogen atom, such as platinum (Pt), iridium (Ir), palladium (Pd), or the like.
  • a material having a catalytic action of dissociating a hydrogen atom from a gas molecule having a hydrogen atom such as platinum (Pt), iridium (Ir), palladium (Pd), or the like.
  • the material of the first electrode 103 include tungsten (W), nickel (Ni), tantalum (Ta), titanium (Ti), aluminum (Al), tantalum nitride (TaN), and titanium nitride (TiN).
  • a material having a lower standard electrode potential than the metal constituting the metal oxide may be used. The standard electrode potential represents a characteristic that the higher the value is, the more difficult it is to oxidize.
  • the substrate 101 for example, a silicon single crystal substrate or a semiconductor substrate can be used, but the substrate 101 is not limited thereto. Since the gas sensitive resistance film 104 can be formed at a relatively low substrate temperature, for example, the gas sensitive resistance film 104 can be formed on a resin material or the like.
  • the gas sensor 100 may further include, for example, a fixed resistor, a transistor, or a diode as a load element electrically connected to the gas sensitive resistance film 104.
  • the gas sensor 100 may include a measurement circuit that measures a current flowing through the gas-sensitive resistive film 104 when a predetermined voltage is applied between the first electrode 103 and the second electrode 106.
  • the gas sensor 100 may include a power supply circuit that constantly applies a predetermined voltage between the first electrode 103 and the second electrode 106. According to such a configuration, a highly convenient gas sensor can be obtained as a module component including a measurement circuit or a power supply circuit.
  • an insulating film 102 having a thickness of 200 nm is formed on a substrate 101 made of, for example, single crystal silicon by a thermal oxidation method. Then, a Pt film having a thickness of 100 nm, for example, is formed on the insulating film 102 as the first electrode 103 by a sputtering method. Note that an adhesion layer of Ti, TiN, or the like can be formed between the first electrode 103 and the insulating film 102 by a sputtering method. Thereafter, an oxygen-deficient metal oxide layer that becomes the gas-sensitive resistive film 104 is formed on the first electrode 103 by, for example, reactive sputtering using a Ta target. Thus, the gas sensitive resistance film 104 is formed.
  • the thickness of the gas-sensitive resistive film 104 if it is too thick, there is a disadvantage that the initial resistance value becomes too high, and if it is too thin, there is a disadvantage that a stable resistance change cannot be obtained. For the above reasons, it may be about 1 nm or more and 8 nm or less.
  • a Pt film having a thickness of 150 nm is formed as the second electrode 106 on the gas-sensitive resistance film 104 by a sputtering method.
  • a photoresist mask 110 is formed by a photolithography process.
  • the first electrode 103, the gas sensitive resistance film 104, and the second electrode 106 are formed in the shape of an element by dry etching using a mask 110.
  • an interlayer insulating film 107 is formed so as to cover the insulating film 102, the first electrode 103, the gas sensitive resistance film 104, and the second electrode 106. Then, a via hole 107 b reaching a part of the upper surface of the second electrode 106 is provided in the interlayer insulating film 107 by etching.
  • a conductor film 708 is formed so as to fill the upper surface of the interlayer insulating film 107 and the inside of the via hole 107b.
  • the conductive film 708 on the interlayer insulating film 107 is removed by CMP (Chemical Mechanical Planarization) to form a via 108 in the via hole 107b.
  • CMP Chemical Mechanical Planarization
  • a new conductor film is disposed on the interlayer insulating film 107 and patterned to form a wiring conductor 109 connected to the via 108.
  • an opening 107a through which a part of the upper surface of the second electrode 106 is exposed is provided in the interlayer insulating film 107 by etching.
  • FIG. 3 is a graph showing resistance change characteristics actually measured with the sample elements.
  • the initial breakdown voltage is set between the first electrode 103 and the second electrode 106.
  • the resistance value changes to the low resistance value LR (step S301).
  • two kinds of voltage pulses having a pulse width of 100 ns and different polarities, that is, a positive voltage pulse and a negative voltage are used as a writing voltage.
  • the resistance value of the gas-sensitive resistive film 104 changes as shown in FIG.
  • the resistance value of the gas sensitive resistance film 104 increases from the low resistance value LR to the high resistance value HR (step S302).
  • the resistance value of the gas sensitive resistance film 104 decreases from the high resistance value HR to the low resistance value LR (step S303).
  • the polarity of the voltage pulse is “positive” when the potential of the second electrode 106 is high with reference to the potential of the first electrode 103, and the second electrode 106 with reference to the potential of the first electrode 103. When the potential of is low, it is “negative”.
  • the hydrogen-containing gas can be detected using the gas sensor 100 set to the high resistance state. Thereby, since the fall of resistance value can be detected more clearly compared with the case where hydrogen content gas is detected using gas sensor 100 of a low resistance state, the detection characteristic of hydrogen content gas improves.
  • FIG. 4 is a cross-sectional view illustrating a configuration example of a gas sensor according to a modification of the first embodiment. Hereinafter, only differences from the gas sensor 100 of the first embodiment will be described.
  • the gas sensor 200 of the present modification includes a first metal oxide layer 204a that is in contact with the first electrode 103 and a first metal oxide layer 204a stacked on a first metal oxide layer 204a. It differs from the gas sensor 100 of 1st Embodiment by the point provided with the 2nd layer with the 2nd metal oxide layer 204b which contact
  • the gas sensitive resistance film 204 is not limited to two layers, and may include three or more metal oxide layers.
  • the first metal oxide layer 204a and the second metal oxide layer 204b include a local region 105 in which the degree of oxygen deficiency reversibly changes depending on the application of an electric pulse and the presence or absence of a hydrogen-containing gas. Yes.
  • the local region 105 penetrates at least the second metal oxide layer 204 b and is in contact with the second electrode 106.
  • the gas-sensitive resistive film 204 includes a stacked structure of a first metal oxide layer 204a including at least a first metal oxide and a second metal oxide layer 204b including a second metal oxide. including.
  • the first metal oxide layer 204a is disposed between the first electrode 103 and the second metal oxide layer 204b, and the second metal oxide layer 204b is the first metal oxide layer. It is arranged between 204 a and the second electrode 106.
  • the thickness of the second metal oxide layer 204b may be smaller than the thickness of the first metal oxide layer 204a. In this case, a structure in which the local region 105 is not in contact with the first electrode 103 can be easily formed.
  • the oxygen deficiency of the metal oxide contained in the second metal oxide layer 204b may be smaller than the oxygen deficiency of the metal oxide contained in the first metal oxide layer 204a. In this case, since the resistance value of the second metal oxide layer 204b is higher than the resistance value of the first metal oxide layer 204a, most of the voltage applied to the gas-sensitive resistance film 204 is the second metal oxide layer 204b. Applied to the physical layer 204b. According to this configuration, for example, the initial break voltage necessary for forming the local region 105 can be reduced.
  • the “oxygen content” is used instead of the “oxygen deficiency”.
  • the term is sometimes used. “High oxygen content” corresponds to “low oxygen deficiency” and “low oxygen content” corresponds to “high oxygen deficiency”.
  • the gas-sensitive resistive film 204 is limited to the case where the metals contained in the first metal oxide layer 204a and the second metal oxide layer 204b are the same. Is not to be done.
  • the metals contained in the first metal oxide layer 204a and the second metal oxide layer 204b may be different metals. That is, the first metal oxide layer 204a and the second metal oxide layer 204b may include different metal oxides.
  • the oxygen content corresponds to the degree of oxygen deficiency. is there. That is, when the oxygen content of the second metal oxide included in the second metal oxide layer 204b is greater than the oxygen content of the first metal oxide included in the first metal oxide layer 204a.
  • the oxygen deficiency of the second metal oxide is smaller than the oxygen deficiency of the first metal oxide.
  • the gas-sensitive resistance film 204 includes a local region 105 in the vicinity of the interface between the first metal oxide layer 204a and the second metal oxide layer 204b.
  • the oxygen deficiency of the metal oxide included in the local region 105 is greater than the oxygen deficiency of the metal oxide included in the second metal oxide layer 204b, and the metal oxide included in the first metal oxide layer 204a. Different from the lack of oxygen.
  • the local region 105 is formed in the gas sensitive resistance film 204 by applying an initial break voltage between the first electrode 103 and the second electrode 106.
  • the initial break voltage is a value between the first electrode 103 and the second electrode 106 in order to reversibly transition the gas sensitive resistance film 204 between the high resistance state and the low resistance state. It is a voltage whose absolute value is larger than the applied voltage.
  • the initial break voltage is a voltage lower than the applied voltage for reversibly transitioning between the high resistance state and the low resistance state, and is repeatedly applied between the first electrode 103 and the second electrode 106. Or may be applied continuously for a predetermined time.
  • Application of the initial break voltage makes contact with the second electrode 106, penetrates the second metal oxide layer 204 b, partially enters the first metal oxide layer 204 a, and makes contact with the first electrode 103. No local region 105 is formed.
  • FIG. 5A is a block diagram illustrating an example of an evaluation system used for evaluation of the gas sensor 200.
  • An evaluation system 900 illustrated in FIG. 5A includes a sealed container 910 that stores the gas sensor 200, a power source 920, and a current measuring device 930.
  • the hermetic container 910 is connected to a hydrogen cylinder 911 and a nitrogen cylinder 912 via introduction valves 913 and 914, respectively, and is configured to be able to discharge internal gas via an exhaust valve 915.
  • FIG. 5B is a graph showing an evaluation example of the gas sensor 200.
  • the horizontal axis represents time (au), and the vertical axis represents the current value (au) flowing between the first electrode 103 and the second electrode 106.
  • nitrogen gas was introduced into the sealed container 910 in which the gas sensor 200 was placed, then the nitrogen gas was switched to hydrogen gas, and then the hydrogen gas was switched to nitrogen gas.
  • FIG. 5B shows the result at this time, and the horizontal axis shows three periods in which the previous nitrogen introduction (step S501), hydrogen introduction (step S502), and the subsequent nitrogen introduction (step S503) were performed.
  • step S501 previous nitrogen introduction
  • step S502 hydrogen introduction
  • step S503 subsequent nitrogen introduction
  • the gas sensor 200 was used in which the local region 105 was set in a high resistance state by applying a predetermined voltage between the first electrode 103 and the second electrode 106 in advance.
  • a detection voltage of 0.6 V is applied between the first electrode 103 and the second electrode 106, and the first electrode 103 and the second electrode are detected while hydrogen gas is detected.
  • a current of 10 to 20 ⁇ A flowed between the electrodes 106. Therefore, according to the gas sensor 200, it can be seen that the hydrogen-containing gas can be monitored with a very small power consumption of 0.006 to 0.012 mW.
  • the inventors infer the hydrogen gas detection mechanism in the gas sensor 200 as follows.
  • This hydrogen atom causes a reduction reaction of the metal oxide in the local region 105, and the degree of oxygen deficiency of the metal oxide contained in the local region 105 increases. As a result, the filaments in the local region 105 are easily connected, and the resistance value of the local region 105 is reduced. As a result, it is considered that the current flowing between the first electrode 103 and the second electrode 106 increases.
  • the filaments in the local region 105 are not easily connected and the resistance value is increased. Thereby, the current flowing between the first electrode 103 and the second electrode 106 is reduced.
  • the above-described operation is not limited to the gas sensor 200, and is considered to occur also in the gas sensor 100 whose main part structure is substantially equal to the gas sensor 200 and other gas sensors described later. Further, the above-described operation is not limited to the case where the gas in contact with the second electrode 106 is hydrogen gas. For example, it is considered that the operation occurs also when the gas is a hydrogen-containing gas such as methane or alcohol.
  • the gas sensor generates heat only by the current for detecting the resistance state, and can detect the hydrogen-containing gas without being heated by a separate heater. Is obtained.
  • the gas sensor according to the second embodiment is a metal-insulating film formed by laminating a gas-sensitive resistive film, which is a metal oxide layer, and a metal film, similarly to the gas sensor according to the first embodiment described above.
  • a gas sensor with a metal (MIM) structure The gas sensor can detect a hydrogen-containing gas without being heated by a heater by utilizing self-heating and gas sensitivity in a local region that is a part of the gas-sensitive resistive film.
  • the hydrogen-containing gas is a general term for gases composed of molecules having hydrogen atoms, and as an example, may include hydrogen, methane, alcohol, and the like.
  • FIG. 6A is a cross-sectional view showing a configuration example of the gas sensor 300 according to the second embodiment.
  • FIG. 6B is a top view showing a configuration example of the gas sensor 300 according to the second embodiment.
  • the cross section in FIG. 6A corresponds to the cross section seen in the direction of the arrow along the cutting line 6A-6A in FIG. 6B.
  • the gas sensor 300 includes a substrate 301, an insulating film 302 disposed on the substrate 301, a first electrode 303, a second electrode 306, a first electrode 303, and a second electrode disposed above the insulating film 302.
  • the first electrode 303 has a first main surface that is a lower surface and a second main surface that is an upper surface.
  • the second electrode 306 has a third main surface that is a lower surface and a fourth main surface that is an upper surface.
  • the second main surface of the first electrode 303 and at least a part of the third main surface of the second electrode 306 are arranged to face each other, and the second main surface of the first electrode 303 and the second main surface A gas sensitive resistance film 304 is disposed in contact with the third main surface of the electrode 306.
  • the interlayer insulating film 307 is provided with an opening 307a for bringing the second electrode 306 into contact with the gas to be inspected.
  • the interlayer insulating film 307 covers the first electrode 303, a part of the second electrode 306, and the gas sensitive resistance film 304, and at least a part of the upper surface of the second electrode 306 is the interlayer insulating film 307. It is exposed to the gas to be inspected without being covered with.
  • the area where the first electrode 303 and the gas sensitive resistance film 304 are in contact is smaller than the area where the second electrode 306 and the gas sensitive resistance film 304 are in contact.
  • the gas sensitive resistance film 304 is disposed between the first electrode 303 and the second electrode 306 in the same manner as the gas sensitive resistance film 104 according to the first embodiment described above. It is a layer that can reversibly transition between resistance states.
  • the resistance state of the gas-sensitive resistive film 304 depends on the voltage applied between the first electrode 303 and the second electrode 306 and the presence or absence of a hydrogen-containing gas in the gas in contact with the second electrode 306. Change.
  • a local region 305 that is in contact with the second electrode 306 and is not in contact with the first electrode 303 is provided.
  • the degree of oxygen deficiency of the metal oxide included in the local region 305 reversibly changes in accordance with the application of an electric pulse applied between the first electrode 303 and the second electrode 306.
  • the metal oxide contained in the local region 305 has a larger oxygen deficiency than the metal oxide contained in a portion other than the local region 305 of the gas sensitive resistance film 304.
  • the local region 305 is a minute region including a filament composed of oxygen defect sites. The filament functions as a conductive path.
  • a via 308 is disposed in a portion of the interlayer insulating film 307 that covers the second electrode 306.
  • the via 308 passes through the interlayer insulating film 307 and is connected to the second electrode 306.
  • a wiring conductor 309 is disposed on the via 308.
  • the local region 305 is easily formed in a region where the electric field of the gas-sensitive resistive film 304 is concentrated. Therefore, when the first electrode 303 is present below the via 308, the region immediately below the via 308 is a region where the local region 305 is relatively easily formed. For example, when the local region 305 is formed immediately below the upper structure such as the via 308, hydrogen atoms dissociated from the hydrogen-containing gas in the second electrode 306 cannot reach the local region 305 in a short time, There is a concern that detection sensitivity and response time may be impaired.
  • the area where the first electrode 303 and the gas sensitive resistance film 304 are in contact with each other is that the second electrode 306 and the gas sensitive resistance film 304 are in contact with each other. Since it is smaller than the area, the outline of the first electrode 303 can be provided at a desired position inside the second electrode 306 in a top view. Therefore, depending on the contour position of the first electrode 303, the local region 305 is formed while avoiding a position where there is a concern that the detection sensitivity and response time may be impaired, for example, directly below the upper structure such as the connection via 308. be able to.
  • the local region 305 By forming the local region 305, for example, below the opening 307a, avoiding directly under the via 308, hydrogen atoms dissociated from the hydrogen-containing gas in the second electrode 306 reach the local region 305 in a short time. That is, in the configuration of the gas sensor 300, the time required for hydrogen atoms to reach the local region 305 from the surface of the second electrode 306 is shorter than the arrival time when the local region 305 is formed immediately below the via 308. . As a result, the gas sensor 300 excellent in responsiveness can be obtained.
  • the resistance change phenomenon and the hydrogen detection mechanism in the gas sensor 300 are the same as the resistance change phenomenon and the hydrogen detection mechanism in the gas sensor 100 of the first embodiment.
  • an insulating film 302 having a thickness of 200 nm is formed on a substrate 301 made of, for example, single crystal silicon by a thermal oxidation method.
  • a Pt film having a thickness of, for example, 100 nm is formed on the insulating film 302 by a sputtering method as the conductor film 713 to be the first electrode 303.
  • an adhesion layer of Ti, TiN, or the like can be formed between the conductor film 713 and the insulating film 302 by a sputtering method.
  • a mask (not shown) made of a photoresist is formed on the conductor film 713 by a photolithography process.
  • the first electrode 303 is formed by dry etching using the mask.
  • an oxygen-deficient metal oxide layer to be the gas-sensitive resistive film 304 is formed on the first electrode 303 by, for example, a reactive sputtering method using a Ta target.
  • the thickness of the gas sensitive resistance film 304 if it is too thick, there is a disadvantage that the initial resistance value becomes too high, and if it is too thin, there is a disadvantage that a stable resistance change cannot be obtained.
  • the thickness of the gas-sensitive resistive film 304 may be about 1 nm to 8 nm.
  • a Pt film having a thickness of, for example, 150 nm is formed as a second electrode 306 on the gas sensitive resistance film 304 by a sputtering method.
  • a mask 310 made of a photoresist is formed on the second electrode 306 by a photolithography process.
  • the gas sensitive resistance film 304 and the second electrode 306 are formed in the shape of an element by dry etching using a mask 310.
  • an interlayer insulating film 307 is formed so as to cover the insulating film 302, the gas sensitive resistance film 304, and the second electrode 306. Then, a via hole 307 b reaching a part of the upper surface of the second electrode 306 is provided in the interlayer insulating film 307 by etching.
  • a conductor film 718 is formed so as to fill the upper surface of the interlayer insulating film 307 and the inside of the via hole 307b.
  • the conductor film 718 on the interlayer insulating film 307 is removed by CMP to form a via 308 in the via hole 307b.
  • a new conductor film is disposed on the interlayer insulating film 307 and patterned to form a wiring conductor 309 connected to the via 308.
  • an opening 307a through which a part of the upper surface of the second electrode 306 is exposed is provided in the interlayer insulating film 307 by etching.
  • the portion corresponding to the outline of the first electrode 303 in the gas sensitive resistance film 304 is seen in a plan view.
  • the local region 305 is formed, and the gas sensor 300 shown in FIG. 6A is completed.
  • the resistance change characteristic due to voltage application of the gas sensor 300 configured in this manner is substantially the same as the resistance change characteristic due to voltage application of the gas sensor 100 shown in FIG. Further, in the gas sensor 300, the resistance change due to the hydrogen-containing gas is generated by the same mechanism as that described for the gas sensor 100. Therefore, hydrogen-containing gas can be detected with low power consumption using the gas sensor 300.
  • FIG. 8 is a cross-sectional view illustrating a configuration example of the gas sensor 400 according to the first modification of the second embodiment. Only differences from the gas sensor 300 of the second embodiment will be described below.
  • the gas sensitive resistance film 404 is laminated on the first metal oxide layer 404a in contact with the first electrode 303 and the first metal oxide layer 404a. It differs from the gas sensor 300 of 2nd Embodiment by the point provided with two layers with the 2nd metal oxide layer 404b which contact
  • the gas sensitive resistance film 404 is not limited to two layers, and may include three or more metal oxide layers.
  • the first metal oxide layer 404a and the second metal oxide layer 404b include a local region 305 in which the degree of oxygen deficiency reversibly changes depending on the application of an electric pulse and the presence or absence of a hydrogen-containing gas. Yes.
  • the local region 305 penetrates at least the second metal oxide layer 404 b and is in contact with the second electrode 306.
  • the metal oxide included in the local region 305 has a larger oxygen deficiency than the metal oxide included in the second metal oxide layer 404b.
  • the gas-sensitive resistive film 404 includes a stacked structure of a first metal oxide layer 404a containing at least a first metal oxide and a second metal oxide layer 404b containing a second metal oxide. including.
  • the first metal oxide layer 404a is disposed between the first electrode 303 and the second metal oxide layer 404b, and the second metal oxide layer 404b is the first metal oxide layer. It is disposed between 404 a and the second electrode 306.
  • the thickness of the second metal oxide layer 404b may be smaller than the thickness of the first metal oxide layer 404a. In this case, a structure in which the local region 305 is not in contact with the first electrode 303 can be easily formed.
  • the oxygen deficiency of the metal oxide contained in the second metal oxide layer 404b may be smaller than the oxygen deficiency of the metal oxide contained in the first metal oxide layer 404a. In this case, since the resistance value of the second metal oxide layer 404b is higher than the resistance value of the first metal oxide layer 404a, most of the voltage applied to the gas-sensitive resistance film 404 is the second metal oxide layer 404b. Applied to the physical layer 404b. According to this configuration, for example, the initial break voltage necessary for forming the local region 305 can be reduced.
  • the gas-sensitive resistive film 404 is not limited to the case where the metals contained in the first metal oxide layer 404a and the second metal oxide layer 404b are the same.
  • the metals contained in the first metal oxide layer 404a and the second metal oxide layer 404b may be different metals. That is, the first metal oxide layer 404a and the second metal oxide layer 404b may include different metal oxides.
  • the oxygen content rate corresponds to the degree of oxygen deficiency. is there. That is, when the oxygen content of the second metal oxide included in the second metal oxide layer 404b is greater than the oxygen content of the first metal oxide included in the first metal oxide layer 404a.
  • the oxygen deficiency of the second metal oxide is smaller than the oxygen deficiency of the first metal oxide.
  • the gas-sensitive resistance film 404 includes a local region 305 in the vicinity of the interface between the first metal oxide layer 404a and the second metal oxide layer 404b.
  • the oxygen deficiency of the metal oxide included in the local region 305 is greater than the oxygen deficiency of the metal oxide included in the second metal oxide layer 404b, and the metal oxide included in the first metal oxide layer 404a. Different from the lack of oxygen.
  • the local region 305 is formed in the gas sensitive resistance film 404 by applying an initial break voltage between the first electrode 303 and the second electrode 306.
  • the initial break voltage is the same as that of the first embodiment, the description thereof is omitted.
  • Application of the initial break voltage makes contact with the second electrode 306, penetrates through the second metal oxide layer 404 b, partially enters the first metal oxide layer 404 a, and makes contact with the first electrode 303. No local region 305 is formed.
  • heat is generated only by the current for detecting the resistance state, and the hydrogen-containing gas can be detected without being heated by a separate heater.
  • FIG. 9 is a cross-sectional view illustrating a configuration example of the gas sensor 500 according to Modification 2 of the second embodiment. Only differences from the gas sensor 300 of the second embodiment will be described below.
  • the gas sensor 500 is the gas in the second embodiment in that the first electrode 503 is embedded in the insulating film 502 and the upper surface of the first electrode 503 and the upper surface of the insulating film 502 are formed flush with each other. Different from the sensor 300. By forming the upper surface of the first electrode 503 and the upper surface of the insulating film 502 on the same plane, the gas-sensitive resistive film 504 and the second electrode 506 above the first electrode 503 are formed in a flat plate shape. Is done.
  • the first electrode 503 has a first main surface that is a lower surface and a second main surface that is an upper surface.
  • the second electrode 506 has a third main surface that is a lower surface and a fourth main surface that is an upper surface.
  • the second main surface of the first electrode 503 and at least a part of the third main surface of the second electrode 506 are arranged to face each other.
  • a gas sensitive resistance film 504 is disposed in contact with the second main surface of the first electrode 503 and the third main surface of the second electrode 506.
  • the metal oxide contained in the local region 505 reversibly changes in oxygen deficiency depending on the application of an electric pulse and the presence or absence of a hydrogen-containing gas.
  • the local region 505 is disposed in contact with the second electrode 506.
  • the metal oxide contained in the local region 505 has a larger oxygen deficiency than the metal oxide contained in a portion other than the local region 505 of the gas sensitive resistance film 504.
  • the local region 505 is a minute region including a filament composed of oxygen defect sites.
  • a groove with a depth of 100 nm for embedding the first electrode 503 is formed.
  • a photolithography technique and a dry etching technique are formed by a photolithography technique and a dry etching technique.
  • a conductor film to be the first electrode 503 for example, a Pt film having a thickness of 200 nm is formed on the insulating film 502 by a sputtering method so as to fill the groove.
  • the Pt film on the upper surface of the insulating film 502 is removed by CMP, leaving the Pt film in the trench, and the upper surface of the insulating film 502 and the upper surface of the first electrode 503 are flush with each other.
  • an adhesive layer of Ti, TiN, or the like can be formed between the first electrode 503 and the insulating film 502 by a sputtering method.
  • an oxygen-deficient metal oxide layer that becomes the gas-sensitive resistive film 504 is formed by, for example, a reactive sputtering method using a Ta target.
  • the thickness of the gas-sensitive resistance film 504 if it is too thick, there is a disadvantage that the initial resistance value becomes too high, and if it is too thin, there is a disadvantage that a stable resistance change cannot be obtained.
  • the thickness of the gas-sensitive resistive film 504 may be about 1 nm to 8 nm.
  • a Pt film having a thickness of, for example, 150 nm is formed as a second electrode 506 on the gas sensitive resistance film 504 by a sputtering method.
  • a mask 510 made of a photoresist is formed on the second electrode 506 by a photolithography process.
  • the gas-sensitive resistance film 504 and the second electrode 506 are formed in the shape of an element by dry etching using a mask 510.
  • an interlayer insulating film 307 is formed so as to cover the insulating film 502, the gas sensitive resistance film 504, and the second electrode 506. Then, a via hole 307 b reaching a part of the upper surface of the second electrode 506 is provided in the interlayer insulating film 307 by etching.
  • a conductor film 718 is formed so as to fill the upper surface of the interlayer insulating film 307 and the inside of the via hole 307b.
  • the conductor film 718 on the interlayer insulating film 307 is removed by CMP to form a via 308 in the via hole 307b.
  • a new conductor film is disposed on the interlayer insulating film 307 and patterned to form a wiring conductor 309 connected to the via 308.
  • an opening 307a through which a part of the second electrode 506 is exposed is provided in the interlayer insulating film 307 by etching.
  • the portion corresponding to the outline of the first electrode 503 in the gas-sensitive resistive film 504 is seen in a plan view.
  • the local region 505 is formed, and the gas sensor 500 shown in FIG. 9 is completed.
  • the resistance change characteristic due to voltage application of the gas sensor 500 configured as described above is substantially the same as the resistance change characteristic due to voltage application of the gas sensor 100 shown in FIG. Also in the gas sensor 500, the resistance change due to the hydrogen-containing gas occurs by the same mechanism as that described for the gas sensor 100. Accordingly, the hydrogen-containing gas can be detected with low power consumption using the gas sensor 500.
  • FIG. 11 is a cross-sectional view illustrating a configuration example of the gas sensor 600 according to Modification 3 of the second embodiment.
  • Modification 3 of the second embodiment.
  • the gas sensor 600 of the present modification includes a first metal oxide layer 604a that is in contact with the first electrode 503 and a first metal oxide layer 604a stacked on a first metal oxide layer 604a. It differs from the gas sensor 500 of the modification 2 of 2nd Embodiment by the point provided with the 2nd metal oxide layer 604b which touches the 2nd electrode 506.
  • the gas sensitive resistance film 604 is not limited to two layers, and may include three or more metal oxide layers.
  • the first metal oxide layer 604a and the second metal oxide layer 604b include a local region 505 in which the degree of oxygen deficiency reversibly changes depending on the application of an electric pulse and the presence or absence of a hydrogen-containing gas. Yes.
  • the local region 505 penetrates at least the second metal oxide layer 604 b and is in contact with the second electrode 506.
  • the gas-sensitive resistive film 604 has a stacked structure of a first metal oxide layer 604a containing at least a first metal oxide and a second metal oxide layer 604b containing a second metal oxide. including.
  • the first metal oxide layer 604a is disposed between the first electrode 503 and the second metal oxide layer 604b, and the second metal oxide layer 604b is the first metal oxide layer. It is disposed between 604a and the second electrode 506.
  • the thickness of the second metal oxide layer 604b may be smaller than the thickness of the first metal oxide layer 604a. In this case, a structure in which the local region 505 is not in contact with the first electrode 503 can be easily formed.
  • the oxygen deficiency of the metal oxide contained in the second metal oxide layer 604b may be smaller than the oxygen deficiency of the metal oxide contained in the first metal oxide layer 604a. In this case, since the resistance value of the second metal oxide layer 604b is higher than the resistance value of the first metal oxide layer 604a, most of the voltage applied to the gas sensitive resistance film 604 is the second metal oxide layer 604b. Applied to the physical layer 604b. According to this configuration, for example, the initial break voltage necessary for forming the local region 505 can be reduced.
  • the gas-sensitive resistive film 604 includes a local region 505 in the vicinity of the interface between the first metal oxide layer 604a and the second metal oxide layer 604b.
  • the oxygen deficiency of the metal oxide included in the local region 505 is greater than the oxygen deficiency of the metal oxide included in the second metal oxide layer 604b, and the metal oxide included in the first metal oxide layer 604a. Different from the lack of oxygen.
  • the local region 505 is formed in the gas sensitive resistance film 604 by applying an initial break voltage between the first electrode 503 and the second electrode 506.
  • the initial break voltage is reversibly between the first electrode 503 and the second electrode 506, and the high resistance state and the low resistance state are reversibly the same as in the first embodiment, and thus the description is omitted.
  • the first electrode 506 is in contact with the second electrode 506, partly penetrates the first metal oxide layer 604 a through the second metal oxide layer 604 b, and is in contact with the first electrode 503. No local region 505 is formed.
  • heat is generated only by the current for detecting the resistance state, and the hydrogen-containing gas can be detected without being heated by a separate heater.
  • the fuel cell vehicle according to the third embodiment includes any one of the gas sensors described in the first and second embodiments and the modifications thereof, and detects hydrogen gas in the vehicle with the gas sensor. To do.
  • FIG. 12 is a side view showing a configuration example of the fuel cell vehicle 800 according to the third embodiment.
  • the fuel cell automobile 800 includes a guest room 810, a cargo room 820, a gas tank room 830, a fuel tank 831, a gas sensor 832, a pipe 840, a fuel cell room 850, a fuel cell 851, a gas sensor 852, a motor room 860, and a motor 861. .
  • the fuel tank 831 is provided in the gas tank chamber 830 and holds hydrogen gas as the fuel gas.
  • the gas sensor 832 detects fuel gas leakage in the gas tank chamber 830.
  • the fuel cell 851 includes a fuel cell stack in which a plurality of cells serving as basic units having a fuel electrode, an air electrode, and an electrolyte are stacked.
  • the fuel cell 851 is provided in the fuel cell chamber 850.
  • Hydrogen gas in the fuel tank 831 is sent to the fuel cell 851 in the fuel cell chamber 850 through the pipe 840. Electric power is generated by reacting the hydrogen gas and oxygen gas in the atmosphere in the fuel cell 851.
  • the gas sensor 852 detects hydrogen gas leakage in the fuel cell chamber 850.
  • the motor 861 is provided in the motor chamber 860. When the motor 861 is rotated by the electric power generated by the fuel cell 851, the fuel cell automobile 800 is caused to travel.
  • the gas sensor according to the present disclosure can detect a hydrogen-containing gas with a very small power consumption of about 0.01 mW as an example. Therefore, it is possible to constantly monitor hydrogen gas leakage without significantly increasing the standby power of the fuel cell vehicle by making use of the excellent power saving performance of the gas sensor.
  • a predetermined voltage is always applied to the gas sensors 832 and 852, and the tank 831 in the gas tank chamber 830 is based on the amount of current flowing through the gas sensors 832 and 852. It may be determined whether or not hydrogen gas is present outside and outside the fuel cell 851 in the fuel cell chamber 850.
  • the gas sensor is driven to determine the presence or absence of hydrogen gas leak after receiving the ignition key operation.
  • the start time of the fuel cell vehicle can be shortened.
  • safety can be improved by continuously monitoring the hydrogen gas leakage.
  • the gas sensor described above further includes a measurement circuit that measures a current flowing through the gas-sensitive resistive film when a predetermined voltage is applied between the first electrode and the second electrode. May be.
  • the gas sensor may further include a power supply circuit that constantly applies a predetermined voltage between the first electrode and the second electrode.
  • a highly convenient gas sensor can be obtained as a module component including a measurement circuit or a power supply circuit.
  • the gas sensor according to the present disclosure is useful as a gas sensor excellent in power saving.
  • the gas sensor according to the present disclosure is useful as a hydrogen sensor used in, for example, a fuel cell vehicle.

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